CN103450933B - A kind of diesel oil hydrogenation modification combined method - Google Patents
A kind of diesel oil hydrogenation modification combined method Download PDFInfo
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Abstract
The present invention relates to a kind of diesel oil hydrogenation modification combined method, first higher quality diesel oil and from after the recycle hydrogen Hybrid Heating of cold high pressure separator first hydrofining reactor reaction, obtain hydrotreated refinery stream after heat exchange cooling, enter cold high pressure separator, carry out gas-liquid separation and obtain gaseous phase materials and liquid material; The hydrogen of gaseous phase materials after desulphurization system desulfurization again through compressor boosting after with more low-quality diesel oil Hybrid Heating after to the second hydro-upgrading reactor, reaction product enters cold high pressure separator after heat exchange cooling, isolated gaseous phase materials as circulating hydrogen to the first hydrofining reactor, the liquid material of liquid material and high-pressure separator is mixed into light pressure separator, obtain liquid product fractionation in product separation column and obtain gas, petroleum naphtha and diesel oil; Present method first hydrofining reactor desulfurization degree reaches requirement, reduces investment and hydrogen consumption; Second hydro-upgrading reactor can ensure to reach sufficiently high cetane value.
Description
Technical field
The present invention relates to a kind of diesel oil hydrogenation modification combined method.
Background technology
Catalytic cracking has the feature of raw material wide accommodation, good economy performance, is widely used at home, but its diesel quality difference (sulphur, nitrogen and aromaticity content are high, and cetane value is low), storage stability are poor.On the other hand, be protection of the environment, the environmental regulation of increasingly stringent is had higher requirement to diesel product quality, defines sulphur content, aromaticity content and cetane value.General refinery is except catalytic diesel oil, also has the diesel component of a large amount of different qualities such as straight-run diesel oil, coker gas oil, for meeting new quality standard, oil refining enterprise must build new diesel hydrotreating unit, diesel component is carried out hydrofining or the upgrading of economical rationality.
For larger refinery, can build and overlap hydrogenation unit more, good for quality straight-run diesel oil, coker gas oil etc. are carried out hydrofining, and catalytic diesel oil etc. lower for cetane value is carried out hydro-upgrading, to meet the specification of full factory diesel oil sulphur content and cetane value.And for the less refinery of scale, build the small-scale hydrogenation unit of two covers, investment is large; Building a set of hydrogenation unit just needs by inferior condition design, and the diesel oil of quality better exists the problem of excessive hydrogenation, and hydrogen consumption is large, unreasonable economically.
Summary of the invention
The object of this invention is to provide a kind of diesel oil hydrogenation modification combined method; Only need to carry out hydrofining for ordinary diesel oil, and the catalytic diesel oil of inferior quality needs while the impurity such as desulfurization nitrogen, increase substantially the requirement of aromatic saturation rate and diesel cetane-number, hydrofining and hydro-upgrading can be carried out by two reactors under different reaction conditionss, the low diesel-fuel cetane number of effective raising quality, has partition zone optimizing reaction conditions, improves the feature of hydrogenated diesel oil quality comprehensively.
A kind of diesel oil hydrogenation modification combined method of the present invention comprises following content:
First higher quality diesel oil and from after the recycle hydrogen Hybrid Heating of cold high pressure separator first hydrofining reactor reaction, obtain hydrotreated refinery stream after heat exchange cooling, enter cold high pressure separator, carry out gas-liquid separation and obtain gaseous phase materials and liquid material.The hydrogen of gaseous phase materials after desulphurization system desulfurization again through compressor boosting after with more low-quality diesel oil Hybrid Heating after to the second hydro-upgrading reactor, reaction product enters cold high pressure separator after heat exchange cooling, isolated gaseous phase materials as circulating hydrogen to the first hydrofining reactor, the liquid material of liquid material and high-pressure separator is mixed into light pressure separator, obtain liquid product fractionation in product separation column and obtain gas, petroleum naphtha and diesel oil.
The good diesel oil of described quality is the diesel oil distillate such as straight-run diesel oil, coker gas oil, hydrogenating desulfurization diesel oil of 150 ~ 370 DEG C, and the diesel oil of inferior quality is the catalytic diesel oil of 150 ~ 370 DEG C.
The first described hydrofining reaction hydrofining operational condition is 4 ~ 10MPa, hydrogen to oil volume ratio 100:1 ~ 500:1, volume space velocity 0.1 ~ 8.0h
-1, temperature of reaction 270 ~ 450 DEG C.
The described preferred operational condition of the first hydrofining reactor is 6 ~ 9MPa, hydrogen to oil volume ratio 200:1 ~ 400:1, volume space velocity 0.5 ~ 4.0h
-1, temperature of reaction 300 ~ 420 DEG C.
The second described hydro-upgrading reactor operating condition is 4 ~ 20MPa, hydrogen to oil volume ratio 100:1 ~ 1500:1, volume space velocity 0.1 ~ 8.0h
-1, temperature of reaction 240 ~ 450 DEG C.
The described preferred operational condition of the second hydro-upgrading reactor is 8 ~ 14MPa, hydrogen to oil volume ratio 300:1 ~ 1000:1, volume space velocity 0.5 ~ 4.0h
-1, temperature of reaction 300 ~ 420 DEG C.
The second described hydro-upgrading reactor is compared with the high 1.0 ~ 4.0MPa of the first hydrofining reactor pressure, and temperature of reaction is high 30 ~ 50 DEG C, hydrogen to oil volume ratio height 100:1 ~ 600:1.
The first described hydrofining reactor and the second hydro-upgrading reactor share a new hydrogen machine and a set of circulating hydrogen compressor system.
The second described hydro-upgrading reactor can use refining and cracking combination catalyst.
The first described hydrofining reactor and the second hydro-upgrading reactor use identical Hydrobon catalyst, or use different hydrogenation catalysts.
A kind of diesel oil hydrogenation modification combined method of the present invention due to the hydrogen hydrogen sulfide content of the second hydro-upgrading reactor very low, hydrogen dividing potential drop is higher, adds employing catalyst for hydro-upgrading, can ensure sufficiently high cetane value increase rate.Meanwhile, the first hydrofining reactor, owing to adopting lower temperature of reaction and pressure, under Hydrofinishing conditions, only carries out the hydrogenation reaction of certain depth, ensures that desulfurization degree reaches requirement, at utmost reduces investment and hydrogen consumption.
Accompanying drawing explanation
Fig. 1 is diesel oil hydrogenation modification combination process schematic flow sheet.
Embodiment
First higher quality diesel oil 1 and reacting in the first hydrofining reaction district 15 from after recycle hydrogen 2 Hybrid Heating of cold high pressure separator 20, obtain hydrotreated refinery stream 3 after heat exchange cooling, enter cold high pressure separator 16, carry out gas-liquid separation and obtain gaseous phase materials 5 and liquid material 4.The hydrogen 6 of gaseous phase materials 5 after desulphurization system 17 desulfurization again through compressor 18 boost after with more low-quality diesel oil 8 Hybrid Heating after to the second hydro-upgrading reaction zone 19, reaction product 9 enters cold high pressure separator 20 after heat exchange cooling, isolated gaseous phase materials is as circulating hydrogen 2 to the first reaction zone, liquid material 10 is mixed into light pressure separator 21 with the liquid material 4 of high-pressure separator 16, obtain liquid product 11 fractionation in product separation column and obtain gas 12, petroleum naphtha 13 and diesel oil 14.
Embodiment
Table 1 stock oil main character
| Project | Straight-run diesel oil | Catalytic diesel oil |
| Flow, ten thousand tons/year | 120 | 80 |
| Density (20 DEG C)/g/ml | 0.8556 | 0.9225 |
| Boiling range scope, DEG C | 180~340 | 180~350 |
| Sulphur content, wt% | 1.55 | 1.81 |
| Aromaticity content, wt% | 22.1 | 58.6 |
| Cetane value | 46 | 23 |
Table 2 Hydrobon catalyst main character
Table 3 embodiment processing condition and reaction result
| Process program | Referencing schemes | Embodiment-1 | Embodiment-2 |
| First reactor | |||
| Stock oil | Medium diesel oil | Straight-run diesel oil | Straight-run diesel oil |
| Hydrogen dividing potential drop, MPa | 10.0 | 6.5 | 6.5 |
| Hydrogen to oil volume ratio | 500:1 | 300:1 | 300:1 |
| Air speed, h -1 | 1.0 | 2.0 | 2.0 |
| Temperature of reaction, DEG C | 360 | 340 | 350 |
| Second reactor | |||
| Stock oil | - | Catalytic diesel oil | Catalytic diesel oil |
| Hydrogen dividing potential drop, MPa | - | 10.0 | 10.0 |
| Hydrogen to oil volume ratio | - | 500:1 | 500:1 |
| Air speed, h -1 | - | 1.5 | 1.5 |
| Temperature of reaction, DEG C | - | 360 | 360 |
| Hydrogenated diesel oil | |||
| Sulphur content, ug/g | 20 | 50 | 20 |
| Aromaticity content, wt% | 22.0 | 23.0 | 20.0 |
| Cetane value | 52.0 | 52.0 | 53.0 |
Can be found out by embodiment above, the pressure due to the second reactor is high and hydrogen hydrogen sulfide content is low, and hydrogen dividing potential drop is higher, can ensure that catalytic diesel oil has sufficiently high aromatic saturation rate.Owing to only needing desulfurization, an anti-required reaction pressure is lower, thus facility investment is reduced.
Claims (4)
1. a diesel oil hydrogenation modification combined method, is characterized in that:
First higher quality diesel oil and from after the recycle hydrogen Hybrid Heating of cold high pressure separator first hydrofining reactor reaction, obtain hydrotreated refinery stream after heat exchange cooling, enter cold high pressure separator, carry out gas-liquid separation and obtain gaseous phase materials and liquid material; The hydrogen of gaseous phase materials after desulphurization system desulfurization again through compressor boosting after with more low-quality diesel oil Hybrid Heating after to the second hydro-upgrading reactor, reaction product enters cold high pressure separator after heat exchange cooling, isolated gaseous phase materials as circulating hydrogen to the first hydrofining reactor, the liquid material of liquid material and high-pressure separator is mixed into light pressure separator, obtain liquid product fractionation in product separation column and obtain gas, petroleum naphtha and diesel oil;
The good diesel oil of described quality is straight-run diesel oil, coker gas oil, the hydrogenating desulfurization diesel oil of 150 ~ 370 DEG C, and the diesel oil of inferior quality is the catalytic diesel oil of 150 ~ 370 DEG C;
The first described hydrofining reactor operational condition is 4 ~ 10MPa, hydrogen to oil volume ratio 100:1 ~ 500:1, volume space velocity 0.1 ~ 8.0h
-1, temperature of reaction 270 ~ 450 DEG C;
The second described hydro-upgrading reactor operating condition is generally 4 ~ 20MPa, hydrogen to oil volume ratio 100:1 ~ 1500:1, volume space velocity 0.1 ~ 8.0h
-1, temperature of reaction 240 ~ 450 DEG C;
The second described hydro-upgrading reactor is than the high 1.0 ~ 4.0MPa of the first hydrofining reactor pressure, and temperature of reaction is high 30 ~ 50 DEG C, hydrogen to oil volume ratio height 100:1 ~ 600:1;
The second described hydro-upgrading reactor uses refining and cracking combination catalyst;
Two described hydrogenators use identical Hydrobon catalyst, or use different hydrogenation catalysts.
2. in accordance with the method for claim 1, it is characterized in that: the first described hydrofining reactor operational condition is 6 ~ 9MPa, hydrogen to oil volume ratio 200:1 ~ 400:1, volume space velocity 0.5 ~ 4.0h
-1, temperature of reaction 300 ~ 420 DEG C.
3. in accordance with the method for claim 1, it is characterized in that: the second described hydro-upgrading reactor operating condition is 8 ~ 14MPa, hydrogen to oil volume ratio 300:1 ~ 1000:1, volume space velocity 0.5 ~ 4.0h
-1, temperature of reaction 300 ~ 420 DEG C.
4. in accordance with the method for claim 1, it is characterized in that: two described reactors share a new hydrogen machine and a set of circulating hydrogen compressor system.
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| CN106947531B (en) * | 2016-01-06 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of method of catalytic hydroconversion containing aromatics diesel |
| CN109694732B (en) * | 2017-10-23 | 2021-02-09 | 中国石油化工股份有限公司 | Process for processing heavy diesel fuel |
| CN109988600B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Flexible hydrogenation modification process for poor diesel oil |
| CN113061461B (en) * | 2021-03-25 | 2023-02-03 | 南京延长反应技术研究院有限公司 | Device and method for improving diesel oil quality |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1160073A (en) * | 1996-01-22 | 1997-09-24 | 凯洛格总公司 | Two-stage hydroprocessing reaction scheme with series recycle gas flow |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1160073A (en) * | 1996-01-22 | 1997-09-24 | 凯洛格总公司 | Two-stage hydroprocessing reaction scheme with series recycle gas flow |
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